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CP302 Separation Process Principles Mass Transfer / Set 1 (Worked) Examples in Mass Transfer by Diffusion in Binary Systems

Example 1: Diffusion through a stagnant gas film


Oxygen is diffusing in a mixture of oxygen-nitrogen at 1 std atm, 25C. Concentration of oxygen at planes 2 mm apart are 10 and 20 volume % respectively. Nitrogen is non-diffusing. (a) Derive the appropriate expression to calculate the flux oxygen. Define units of each term clearly. (b) Calculate the flux of oxygen. Diffusivity of oxygen in nitrogen = 1.89x10 5 m 2/sec. Solution: Let us denote oxygen as A and nitrogen as B. Flux of A (= N A) is made up of two components, namely that resulting from the bulk motion of A (= Nx A) and that resulting from molecular diffusion J A: N A = Nx A + J A (1.1) From Ficks law of diffusion, J A = D AB Substituting (1.2) in (1.1), we get

dCA dz d CA dz

(1.2) (1.3)

N A = Nx A D AB

Since N = N A + N B and x A = C A / C, (1.3) becomes N A = N A + N B

)C C

D AB

dCA dz

Rearranging the terms and integrating between the planes between 1 and 2,

CD

dz
AB

C A2

C A1

N AC C A ( N A + N B )

dC A

(1.4)

Since B is non-diffusing N B = 0. Also, the total concentration C remains constant. Therefore, (1.4) becomes
C A2 dC A z = C A1 N C N C CD AB A A A

C C A2 1 ln NA C C A1

Therefore,

NA =

CD AB z

ln

C C A2 C C A1 Pt p A2 Pt p A1

(1.5)

Replacing concentration in terms of pressures using Ideal Gas law, (1.5) becomes

NA =
where

D AB Pt RTz

ln

(1.6)

DAB = molecular diffusivity of A in B Pt = total pressure of system R = universal gas constant T = temperature of system in absolute scale z = distance between two planes across the direction of diffusion pA1 = partial pressure of A at plane 1, and pA2 = partial pressure of A at plane 2 Given are DAB = 1.89x10 5 m2/sec; Pt = 1 atm = 1.01325x105 N/m2; T = 25C = 298 K; z = 2 mm = 0.002 m; pA1 = 0.2x1 = 0.2 atm; pA2 = 0.1x1 = 0.1 atm

Substituting these in (1.6), we get,

NA =

(1.89 *10 )(1.01325 *10 ) ln 1 0.1 = 4.55x10


5 5

( 8314 ) ( 298) ( 0.002 )

1 0.2

kmol/m 2.sec

Example 2: Equimolar counter diffusion


Obtain the expression describing the molar flux for steady-state equimolar counter diffusion and its concentration profile. Solution: The molar flux NA, for a binary system at constant temperature and pressure is described by

N A = (N A + N B ) N A = D AB
Z2

CA C

D AB

dCA dz

(2.1)

Equimolar counter diffusion is given by NA = - NB, which reduces (2.1) to

d CA dz
C A2 AB

(2.2)

For steady state diffusion, (2.2) may be integrated, using the boundary conditions as

NA
which gives

Z1

dz = D

C A1

dC

D AB (C A1 C A2 ) z2 z1 n p CA = A = A For ideal gases, V RT D AB ( PA1 PA2 ) Therefore, (2.3) becomes N A = R T ( z2 z1 ) NA =


(2.3) and (2.4) are equations describing the molar flux for steady-state equimolar counter diffusion. Concentration profile in the equimolar counter diffusion may be obtained from

(2.3)

(2.4)

From (2.2), Therefore,

d ( N A ) = 0 (Since NA is constant over the diffusion path). dz d CA N A = D AB dz d dz d CA D AB = 0 dz zz1 z1 z 2


or

d 2 CA = 0. dz2

This equation may be solved using the boundary conditions to give

C A C A1

C A1 C A2

(2.5)

(2.5) indicates a linear concentration profile for equimolar counter diffusion.

Example 3:
Methane diffuses at steady state through a tube containing helium. At point 1 the partial pressure of methane is pA1 = 55 kPa and at point 2, 0.03 m apart, pA2 = 15 KPa. The total pressure is 101.32 kPa, and the temperature is 298 K. At this pressure and temperature, the value of diffusivity is 6.75x10 5 m 2/sec. (a) Calculate the flux of CH 4 at steady state for equimolar counter diffusion. (b) Calculate the partial pressure at a point 0.02 m apart from point 1.

Solution: For steady state equimolar counter diffusion, molar flux is given by

NA =
Therefore,

D AB RT z

(p

A1

p A2 ) = 3.633 10 5 kmol m 2 sec

(3.1)

NA =

6.75 10 5 ( 55 15) kmol 8.314 298 0.03 m 2 sec 6.75 10 5 (55 p A ) 8.314 298 0.02

And from (3.1), partial pressure at 0.02 m from point 1 is calculated as follows:

3.633 10 5 =

p A = 28.33 kPa

Example 4:
In a gas mixture of hydrogen and oxygen, steady state equimolar counter diffusion is occurring at a total pressure of 100 kPa and temperature of 20C. If the partial pressures of oxygen at two planes 0.01 m apart, and perpendicular to the direction of diffusion are 15 kPa and 5 kPa, respectively, and the mass diffusion flux of oxygen in the mixture is 1.6x10 5 kmol/m 2.sec, calculate the molecular diffusivity for the system. Solution: For equimolar counter current diffusion, where NA = molar flux of A (1.6x10 5 kmol/m 2.sec) DAB = molecular diffusivity of A in B R = Universal gas constant (8.314 kJ/kmol.k) T = Temperature in absolute scale (273 + 20 = 293 K) z = distance between two measurement planes 1 and 2 (0.01 m) PA1 = partial pressure of A at plane 1 (15 kPa); and PA2 = partial pressure of A at plane 2 (5 kPa) Substituting these in (4.1), we get Therefore, DAB = 3.898x10 5 m 2/sec

NA =

D AB RTz

(p

A1

p A2 )

(4.1)

1.6 10 5 =

( 8.314 ) ( 293) ( 0.01)

D AB

(15 5)

Example 5:
A tube 1 cm in inside diameter that is 20 cm long is filled with CO2 and H2 at a total pressure of 2 atm at 0C. The diffusion coefficient of the CO2 H2 system under these conditions is 0.275 cm2/sec. If the partial pressure of CO2 is 1.5 atm at one end of the tube and 0.5 atm at the other end, find the rate of diffusion for the following cases: i) steady state equimolar counter diffusion (N A = - N B) ii) steady state counter diffusion where N B = -0.75 N A, and iii) steady state diffusion of CO2 through stagnant H2 (NB = 0) Answers: Denote CO2 by A and H2 by B. i) N A = 6.138x10-6 kmol/m2.sec; Rate of diffusion of A ii) N A = 7.028x10-6 kmol/m2.sec; Rate of diffusion of A iii) N A = 1.349x10-5 kmol/m2.sec; Rate of diffusion of A

= 1.735x103 mol/hr = 1.987x103 mol/hr = 3.814 mol/hr

CP302 Separation Process Principles Mass Transfer / Set 1 (Worked) Examples in Mass Transfer by Diffusion in Binary Systems continued
Example 6:
Water in the bottom of a narrow metal tube is held at T = 293 K. For air, P = 1.01325x105 Pa (= 1 atm) and T = 293 K. Water evaporates and diffuses through the air in the tube and z = 0.1524 m. Calculate the rate of evaporation at steady state in kmol/s.m2. The diffusivity of water vapour in air at 293 K and 1 atm pressure is 0.250x10 -4 m2/s. Assume that the system is isothermal.

Example 7: Diffusion in Liquids


Calculate the rate of diffusion of butanol at 20C under unidirectional steady state conditions through a 0.1 cm thick film of water when the concentrations of butanol at the opposite sides of the film are 10% and 4% butanol by weight, respectively. The diffusivity of butanol in water solution is 5.9x106 cm2/sec. The densities of 10% and 4% butanol solutions at 20C may be taken as 0.971 and 0.992 g/cc, respectively. Molecular weight of butanol (C4H9OH) is 74, and that of water is 18. Solution: Equation derived for diffusion in gases equally applies to diffusion in liquids with some modifications. Mole fraction in liquid phases is normally written as xA = CA/C and the concentration term, C, is replaced by average molar density,

. M av

a) For steady state equimolar counter diffusion, N A = - N B = const

NA=

D D AB ( C A1 C A2 ) = AB C ( x A1 x A2 ) = D AB ( x A1 x A 2 ) z z z M av

(7.1)

b) For steady state diffusion of A through non diffusive B, N A = constant and N B = 0 D AB NA= ( x A1 x A2 ) z x B ,lm M av x B 2 x B1 x B ,lm = where z = z2 z1, the length of diffusion path; and x ln B 2 x B1

(7.2)

(7.3)

To calculate the rate of diffusion of A (butanol) under steady state unidirectional diffusion, use (7.2). Conversions from weight fraction the mole fraction give the following:

x A1 =

( 0.1 74 + 0.9 18)

( 0.1 74 )

= 0.026

and

x A2 =

( 0.04 74 + 0.96 18)

( 0.04 74 )

= 0.010

Average molecular weight at 1 & 2 are given by the following:

M1 =

1 = 19.47 kg kmol ( 0.1 74 + 0.9 18)

and

M2 =

1 = 18.56 kg kmol ( 0.04 74 + 0.96 18)

( 1 M 1 + 2 M 2 ) 0.971 19.47 + 0.992 18.56 = = = 0.0517 mol cm 3 = 51.7 k mol m 3 M av 2 2


4

(7.3) gives,

x B ,lm =

(1 x A2 ) (1 x A1 ) x B 2 x B1 = ln ( x B 2 x B1 ) 1 x A2 ln 1 x A1
D AB ( x A1 x A2 ) 2 M avg x B , lm

(1 0.01 ) (1 0.026 )
1 0.01 ln 1 0.026

0.016 = 0.982 0.0163

Therefore N A =

5.9 10 6 10 4 51.7 ( 0.026 0.010 ) 0.1 10 2 0.982 kmol g gmol = 1.789 74 g = 4.97 10 7 2 = 132.4 2 = 1.789 2 2 m sec m hr m hr m hr = Example 8: Diffusion through a stagnant air film (past paper question)
A circular tank 6 m in diameter contains benzene at 22 oC, which is exposed the atmosphere for 6 hours per working day in such manner that the liquid is covered with a stagnant air film estimated to be 5 mm thick. The concentration of benzene beyond the stagnant air film is negligible. The vapour pressure of benzene at 22oC is 100 mm Hg. if a litre of benzene costs Rs 1500/=, estimate the daily loss due to evaporation of benzene. The specific gravity and diffusivity of benzene at storage conditions are 0.88 and 0.299x2.581x10 -5 m2/s, respectively. Molecular weight of benzene is 78 kg/kmol. Universal gas constant is 8.314 kJ/kmol.K. The atmospheric pressure may be taken as 1.013 bar. (1 bar = 100 kN/m2 = 750 mm Hg)

Example 9: Diffusion through a stagnant air film (past paper question)


A pool of water 1 mm in depth lies on a horizontal surface in contact with dry air at 20 oC and 1 atm. Evaporation takes place and can be treated as molecular diffusion through a 5 mm thick film of moist air immediately above the water surface. Above this gas film, water vapour is assumed to be perfectly mixed with the surrounding (with the zero partial pressure). Assuming that evaporation does not affect the temperature of water, calculate (i) the molar flux of water vapour from the surface, and (ii) the time taken for complete evaporation of the liquid. Diffusivity of water in air can be taken as 2.6x10 -5 m2/s, saturated vapour pressure of water at 20 oC as 2340 N/m2 and gas constant as 8314 J/kmol.K.